Zur Kenntnis der kolloidchemischen Eigenschaften des Humus

Ohne ZusammenfassungMeinem verehrten Lehrer, Herrn Prof. Dr. H. Pallmann — auf dessen Anregung diese Arbeit ausgeführt würde — möchte ich für die mir zuteil gewordene Förderung und die wertvollen Ratschläge bestens danken.     

Specific carbon-13 labelling of leucine residues in human growth hormone.

Biosynthetic human growth hormone specifically 13C-labelled in the carbonyl positions of all 26 leucine residues has been obtained by recombinant DNA techniques using 13C-labelled leucine and an E. coli strain that requires leucine. It is shown that, on the whole, the labelling is specific with no significant mislabelling as would have been the case had the 13C-labelled leucine been metabolized.     

Electron screening in backward elastic scattering

Abstact: The elastic scattering cross sections, σ (E,θ), for the systems He+Ta and He+W have been measured at θ_lab=165° and E _lab=76.1 keV to 3.988 MeV using targets with a thickness of a few atomic layers. The results are smaller than the results given by the Rutherford scattering law, σ_R(E,θ), due to the effects of electron screening and can be described by σ(E,θ)/σ_R(E,θ)=(1+U_e/E)⁻¹, where U _e is an atomic screening potential energy. The deduced average value, U _e=28 ± 3 keV, is consistent with the Moliére- and Lenz-Jensen-models as well as electron binding energies. Received: 25 May 1998     

Structure determination of a key intermediate of the enantioselective Pd complex catalyzed allylic substitution reaction

The structure of a catalytic intermediate with important implications for the interpretation of the stereochemical outcome of the palladium complex catalyzed allylic substitution with phosphino-oxazoline (PHOX) ligands is determined by liquid state NMR. The complex displays a novel structure that is highly distorted compared with other palladium eta2-olefin complexes known so far. The structure has been determined from nuclear overhauser data (NOE), scalar coupling constants, and long range projection angle restraints derived from dipole dipole cross-correlated relaxation of multiple quantum coherence. The latter restraints have been implemented into a distance geometry protocol. The projection angle restraints yield a higher precision in the determination of the relative orientation of the two molecular moieties and are essential to provide an exact structural definition of the olefinic part of the catalytic intermediate with respect to the ligand.     

A regularization approach for damage models based on a displacement gradient

Common material models that take into account softening effects due to damage encounter the problem of ill-posed boundary value problems if no regularization is applied. This condition leads to a non-unique solution for the resulting algebraic system and a strong mesh dependence of the numerical results. A possible solution approach to prevent this problem is to apply regularization techniques that take into account the non-local behavior of the damage [1]. For this purpose a field function is used to couple the local damage parameter to a non-local level, in which differences between the local and non-local parameter as well as the gradient of the non-local parameter can be penalized. In contrast, we present a novel approach to regularization in which no field function is needed [2]. Hereto, the regularization is carried out by means of the divergence of the displacements and no additional quantity is necessary since the displacements are already defined on a non-local level. The idea is that with an increasing value of the damage the element's volume will increase as well. This is a result of the softening due to the occurring damage. The increasing volume can be measured by the divergence of the displacements which can be penalized by an additional energy part. The lack of any field function and the regularization by the use of the divergence of the displacements entails several numerical advantages: the computational effort is considerably reduced and the convergence behavior is improved as well. Naturally, the numerical results are mesh independent due to the regularization. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Development of Novel Isoindolone-Based Compounds against Trypanosoma brucei rhodesiense

This study identified the isoindolone ring as a scaffold for novel agents against Trypanosoma brucei rhodesiense and explored the structure-activity relationships of various aromatic ring substitutions. The compounds were evaluated in an integrated in vitro screen. Eight compounds exhibited selective activity against T. b. rhodesiense (IC₅₀<2.2 μm ) with no detectable side activity against T. cruzi and Leishmania infantum. Compound 20 showed low nanomolar potency against T. b. rhodesiense (IC₅₀=40 nm ) and no toxicity against MRC-5 and PMM cell lines and may be regarded as a new lead template for agents against T. b. rhodesiense. The isoindolone-based compounds have the potential to progress into lead optimization in view of their highly selective in vitro potency, absence of cytotoxicity and acceptable metabolic stability. However, the solubility of the compounds represents a limiting factor that should be addressed to improve the physicochemical properties that are required to proceed further in the development of in vivo-active derivatives.     

Analysis of Non-innocence of Phosphaquinodimethane Ligands when Charge and Aromaticity Come into Play

Several phosphaquinodimethanes and their M(CO)₅ complexes (M=Cr, Mo, W) and model derivatives have been theoretically investigated regarding the quest of non-innocence. Computed structural and electronic properties of the P-Me/NH₂ substituted phosphaquinodimethanes and tungsten complexes revealed an interesting non-innocent ligand behaviour for the radical anion complexes with distonic ion character and a strong rearomatization of the middle phenyl ring. The latter was further probed taking also geometric aromaticity (HOMA) and quinoid distortion parameters (HOMQc) into account, as well as NICS(1). Furthermore, the effect of the P-substitution was investigated for real (or plausible) complexes and their free ligands focusing on the resulting aromaticity at the middle phenyl ring and vertical one-electron redox processes. The best picture of ligand engagement in redox changes was provided by representing NICS(1) values versus HOMA and the new geometric distortion parameter HOMQc8.